Quaternary ammonium-tertiary amine oxide compositions



United States Patent No Drawing. Filed Oct. 21, 1965, Ser. No. 500,282 13 Claims. (Cl. 252-106) This application is a continuation-in-part of application Serial No. 339,307 filed January 21, 1964, now abandoned.

The present invention has for its object the provision of a composition for simultaneously cleaning, softening and sanitizing fabrics and cleaning and santizing walls, floors and other inanimate objects, and which is also capable of cleaning and degerrning human skin and other tissues to a very low level by a single scrub application. It is a further object of this invention to provide a composition for use for this purpose which comprises a tertiary amine oxide and a microbiologically active quaternary ammonium salt.

In particular, it is an object of this invention to provide a composition and process for simultaneously cleaning and effectively degerming, and also for deodo-rizing, human skin and other tissues, such as hair and the like by a single scrub application.

Specifically, it is an object of this invention to provide a composition for simultaneously cleaning and greatly reducing the incidence of microbial fiora on human skin and other tissues for the purpose of antisepsis.

It is most particularly an object of this invention to very significantly reduce the microbial population on the skin upon the very first scrub application, rather than as a result of continued repeated use over a prolonged period.

Other objects of this invention will become apparent from the following description.

Certain quaternary ammonium salts are well known and widely used because of their microbiological activity. Such compounds have in common a long alkyl radical containing from 8 to 20 carbon atoms attached either directly or indirectly through a benzyl group or a phenoxyethoxyethyl group to the nitrogen atom of the quaternary ammonium compound. They will be defined in greater detail hereinafter.

Such quaternary ammonium compounds exhibit, however, certain drawbacks in that they are chemically and microbiologically incompatible with anionic surface active agents, that is to say, when combined in solution with anionic surfactants they are precipitated and/0r deactivated microbiologically. Non-ionic detergents of the ethylene oxide adduct type are utilized in combination with quaternary ammonium germicides in various commercially available detergent sanitizers, but such detergent sanitizers all suffer from rather serious restrictions in the permissible ratio of non-ionic detergent to quaternary ammonium compound. The customary ratio of these two components is usually in the order of 1.5 1. If this value is exceeded, the germicidal activity of the quaternary ammonium compound is impaired until at high ratios such, for example, as 3 or above, the microbiological activity of the quaternary ammonium compound is completely vitiated. Inasmuch as the use concentration of quaternary ammonium compound is normally between 400 to 600 parts per million, the aforementionedlimitation with respect to the permissible amount of non-ionic places a severe restriction on the amount of non-ionic detergent which can be utilized in such detergent sanitizers at use dilutions, thus making these materials unsuitable for adequate cleaning.

Furthermore, although amphoteric detergents have 3,296,145 Patented Jan. 3, 1967 ice been combined with quaternary ammonium compounds, such combinations are particularly effective on the acid side under which condition the amphoteric mate-rial exists in the form of a cationic surfactant. Under alkaline conditions, the amphorteric being in the nature of an anionic surfactant is incompatible with quaternary ammonium germicides.

Hence, it will be apparent that there is a vital need for a satisfactory composition which will both clean and sanitize under wide conditions of acidity and alkalinity and throughout wide ratios of detergent to sanitizer.

We have found that quaternary ammonium compounds can be combined with tertiary amine oxides of the type hereinafter set forth over a wide range of pH and throughout a wide range of ratios of one component to another without any deleterious effect on the microbiological activity of the quarternary ammonium compound. Amine oxides of the alkyl dimethyl amine oxide family in which the alkyl radical contains from 8 to 20 carbon atoms have been described in USP 2,169,976 and until recently have been considered to be cationic in nature. We have found, however, that these materials are not truly cationic and that, contrary to certain assumptions made in the literature without experimental evidence, these amine oxides of themselves possess no germicidal activity. We have found, for example, that lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, stearyl dimethyl amine oxide and oleyl dimethyl amine oxide of themselves all possess no microbiological activity measurable as phenol coefficient by the standard method described in the Official Methods of Analysis of the Association of Ofiicial Agricultural Chemists, Ninth Edition (1960), page 63 et seq. When runagainst Staphylococcus aureaus and Salmonella typhosa, none of these compounds just listed exhibited any appreciable phenol coeflicient.

It has moreover, recently been found that amine oxides of the alkyl dimethyl amine oxide class are compatible with many anionic detergents. Hence, it is suprising that these materials are both physically and microbiologically completely compatible in all proportions and under all condtions of pH with quaternary ammonium compounds.

Up to the present time, there has been no satisfactory method for washing, softening, and sanitizing fabrics in a single operation. It has been necessary to conduct these operations singly or, at best, in at least two different operations because of the incompatibility of the customary anionic detergents and fabric softeners which are cationic in nature. Moreover, the satisfactory sanitization of fabrics, especially diapers, requires the use of cationic germicides which are also incompatible with anionic detergents so that there is precipitation in the bath when they and anionics are used together, with resultant bateriological inactivation of the solution. Moreover, compatibility problems, especially microbiological in nature, arise as hereinabove described when a non-ionic is used as the sole detergent in combination with relatively small amounts of quaternary ammonium germicides.

The compositions comprising said tertiary amine oxides and said microbiologically active quaternarw ammonium salts may also be used as surgical scrub soaps of exceptional effectiveness by a single use. They may also be employed in shampoos for the control of dandruff; or as deodorant soaps; or as detergents for any condition wherein it is desired to reduce or control the bacterial or fungal population of the skin or related tissue.

In addition to pre-operative scrubbing, these compositions are of value in many other fields where the bacterial count of an individuals skin should or must be kept low, for example in food handling in such fields among others as meat-packing, egg-breaking and the like; in nursing, and particularly in baby nursing; by mechanics and others who are subject to cuts, abrasions and other skin injuries which are likely to result in infection; for such cosmetic conditions as acne or boils; and in general wherever it is desirable to employ a degerming washing medium to reduce the incidence or prevent the transmission of infection in, on, to or from the skin or related tissue.

In addition to the cleansing and sanitizing effects of the compositions of this invention, there also obtains the well-known emollient effect upon the skin which is characteristic of the tertiary amine oxides which are employed as components of these compositions. Since the said compositions are effective over a wide pH range, they may be employed in the normal, slightly acid range of the skin. This is a marked contrast to the harsh effect upon tissues of strong or alkaline soaps and of synthetic detergents which effectively remove the natural lubricant oils of those tissues.

The amine oxides which we employ according to the present invention are alkyl dimethyl amine oxides in which the alkyl radical contains from 8 to 20 carbon atoms and correspond to the general formula where R contains from 8 to 20 carbon atoms and may, if desired, be unsaturated in nature, where R and R" may be methyl, ethyl, propyl, isopropyl, hydroxyethyl, hydroxyethoxyethyl, or hydroxyethyl polyethoxyethyl radicals and wherein the oxygen is linked to nitrogen by means of a semi-polar bond. If desired, R' and R" may jointly constitute the CH CH OCH CH radical, i.e. the above formula is:

OHz-CHz lk O CH2CH2 While all of these amine oxides have detersive power, those containing fourteen carbon atoms, or less, are also good foaming agents whereas those possessing 16 carbon atoms, or more, are poor foaming agents.

As suitable quaternary ammonium compounds which- We may use in the compositions of this invention, we may employ any water-soluble quaternary ammonium salt having a long alkyl radical containing from 8 to 22 carbon atoms attached either directly to the nitrogen atom or through an intermediate benzyl or phenoxyethoxyethyl radical and having a phenol coefficient of at least 100 with respect to the Staphylococcus aureus and Salmonella typhosa at 20 C. when determined by the standard method given in the Oflicial Method of Analysis of the Association of Oflicial Agricultural Chemists, Ninth Edition (1960), page 63 et seq. Typical examples of these quaternary ammonium compounds are alkyl trimethyl ammonium chlorides, alkyl-benzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl dimethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted-benzyl ammonium chlorides in which the benzyl radical is substituted with one or more side chains containing from 1 to carbon atoms such, for example, as methyl, dimethyl, ethyl, isopropyl, terbutyl, n-amyl, isoamyl, tetramethyl, trimethyl and the like in which the carbon atoms may all be in the same or different side chains or in which the benzyl radical may be substituted by an alkylene group such as tetrahydro menaphthyl or in which the benzyl radical bears one, two or more halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, alkyl isoquinolinium chlorides and bromides, alkyl lower-alkyl pyrrolidinium chlorides, alkyllower-alkyl moipholinium chlorides in all of which the alkyl group may have from 8 to 22 carbon atoms and the lower-alkyl group may have from 1 to 4 carbon atoms and alkyl phenoxyethoxyethyl dimethylbenzyl ammonium chloride in which the alkyl radical may be iso-octyl or nonyl and in which the benzyl radical may, if desired, be substituted by a methyl radical, Various other analogs of these quaternaries may also be employed such, for example, as cetyl dimethyl ethyl ammonium bromide or oleyl dimethyl ethyl ammonium bromide. Instead of the foregoing chlorides, we may also employ the cor-responding bromides, methosulfates, ethosulfates or other water-soluble analogs. We may also employ mixtures of two or more of the foregoing quaternary ammonium compounds. In particular, we prefer to employ a mixture of alkyl dimethyl benzyl ammonium chloride in which the alkyl radical blend contains at least 50% myristyl, together with alkyl dimethyl ethyl-benzyl ammonium chloride in which the alkyl radical blend is predominantly (at least 50%) C this blend being employed in approximately 1:1 ratio by weight.

We prefer to use the quaternary ammonium compounds which have phenol coefiicients of more than 500 against Staphylococcus aureus; such for example are BTC824, an alkyl dimethyl benzyl ammonium chloride in which lS C14, C16, C12 and C13; TClII'O- san 3,4 D, an alkyl dimethyl dichlorobenzyl ammonium chloride in which the alkyl is 50% Cu, 30% C 17% C and 8% C ETC-471 and ETC-927, which are, respectively, alkly dimethyl ethyl-benzyl and alkyl dimethyl dimethylbenzyl ammonium chlorides in which the alkyl distribution is the same as in Tetrosan 3,4 D; lauryl dimethyl menaphthyl or tetrahyclromenaphthyl ammonium chloride; lauryl isoquinolinium bromide and the like; or mixtures thereof. The aforesaid products are sold by Oynx Chemical Corporation under the previously mentioned trademark designations.

The compositions of this invention are preferably prepared as liquids for convenient use as a surgical or other degerming scrub soap. However, if desired they may be thickened by certain additives into a gel or a paste or to be molded into a bar by methods well known to the art; or they may be prepared as a powder, as for example as an adduct with urea, by mixing the composition with crystalline urea in suflicient amounts to produce a freeflowing powder.

When used for cleaning inanimate objects, they may contain other appropriate adjuvants such, for example,

as alkaline builders including the various phosphates such as trisodium phosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, sodium tripolyphosphate, borax, sodium silicate, sodium carbonate, sodium bicarbonate, sodium sulfate and the like.

In addition to cleaning fabrics, they may be used, for

example, in scrub soaps, for cleaning floors and walls of hospitals; they may be used in dairy sanitation; they may, be used as detergent sanitizers in bars and restaurants and have general janitorial maintenance purposes.

They may also be used in a wide variety of detergents destined for home use such, for example, as in dishwashing compounds and in detergents for both heavy and light duty laundry operations. Such compositions may also be employed for various cosmetic uses, particularly for hair shampoos by means of which the hair is not only cleansed but also left in a static-free, smooth and glossy condition.

The anti-bacterial effectiveness of deodorant toilet bars as well as liquid antiseptic or germicidal hand scrubs ispredominately based on the principle that the active agent gradually builds up on the skin after repeated use, re-, Bacterial upon the Price multiple basin technique. (P. B. Price, Journal of the American Medical Association, 3 (22), pp. 1993-96, November 26, 1938). The Cade modification of the Price method is quite frequently used; briefly, it consists of determining an initial count in a series of five washes; after 5, 11, and 12 days use of the test soap, additional counts are made to follow the course of the reduction of bacteria on the skin. (A. R. Cade, Soap and Sanitary Chemicals, 26, pp. 35-38, 73, July 1950.)

A split-glove technique proposed by Quinn serves to considerably shorten the above techniques and has the distinct advantage that each subject serves as his own control. (H. Quinn et al., Applied Microbiology, 2, pp. 202-4, 1954.) In brief, the subject has one hand covered with a glove and washes the other with the control soap. After rinsing in the basin, the glove is removed, a fresh one is placed on the other hand, and the procedure is repeated with the test soap, in another basin.

In all of these methods, following accurate time intervals for lathering and rinsing and performing each successive wash in a separate basin, the bacterial counts should show a definite decrease with each succeeding wash. The first basin generally shows a high count which consists of transient bacteria, the amount and types of which may vary due to environmental conditions. The bacteria removed with succeeding washes were described by Price as resident bacteria, capable of thriving on skin or whose normal habitat can be considered to be skin. The word degermation is used to designate reduction in these tests of the total number of bacteria present, irrespective of whether the organisms are or are not pathogemc.

6 to be gained is that any given isolated application will immediately provide the desired result. Whether used by workers in a food handling plant or by a surgeon or a dentist, the first wash will significantly reduce the bacterial flora on the skin-not only the transient, but also the resident bacteria.

In practice, it is virtually impossible to expect the continued and uninterrupted use by an individual of any single agent whose activity depends upon just such process. It is also a fact that alcohol or ordinary soap or detergents can completely remove any residual film of such antiseptic agent. The advantages of the product of this invention are therefore evident.

While not limited thereto, the invention will be apparent from the following illustrative examples:

Example I A 30% viscous solution of stearyl dimethyl amine oxide was combined with varying amounts of a active solution of alkyl dimethyl benzyl ammonium chloride in which the alkyl distribution corresponded to 60% C 30% C 5% C 5% C and an equal amount of alkyl dimethyl ethylbenzyl ammonium chloride in which the alkyl distribution corresponded to 50% C 30% C 17% C 3% C The ratios were adjusted so that the proportion of amine oxide to quaternary ammonium germicide on a 100% active basis ranged from about 50:1 to about 5:1 and the pHs of the solutions on an as is basis all varied from 4.0 to 11.0.

The composition of the preparations in the following and subsequent examples is given in parts by weight:

TABLE I A B C D E F G H I Composition:

stearyl dimethyl amine oxide, 30% 40. 0 40. 0 40. 0 34. 0 34. 0 34. 0 17. 0 17. 0 17. 0 Alkyl dimethyl benzyl ammonium chloride, 50% 0.25 0.25 0.25 1.0 1.0 1.0 1.0 1. 0 1.0 .Alkyl dimethyl ethyl-benzyl ammonium chloride, 50%. 0.25 0. 25 0. 25 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 Water Balance pH 11.0 I 7.0 4.0 111.0 7.01 4.01110. 7.0 4.0

1 Alkyl distribution: 60% C 30% C 5% C 5% C". 2 Alkyl distribution: 50% C 30% C 17% C, 3% C Hexachlorophene, trichlorocarbanilides, and bromo salicylanilides which are in widespread use all depend on repeated and constant use for lowering bacterial flora on the skin. Products based on these materials state this very fact in their literature. The Phisohex (trademark, Winthrop Laboratories, New York, N.Y., Brochure 5 828, July 1963) brochure indicates that cumulative and germcontrolling properties are maintained with the constant and exclusive use of the product, which is a sudsing emulsion containing entsufon, lanolin cholesterols, petrolatum and 3% hexachlorophene, otherwise 2,2 methylenebis (3,4,6 trichlorophenol). The manufacturer states that patients scheduled to undergo elective surgery should wash the operative site daily for 510 days before operation. The Septisol (trademark, Vestal Laboratories, St. Louis, Missouri, of which the active ingredients comprise 0.75% of hexachlorophene and 2% of anhydrous soap) label indicates that the product is not intended for antiseptic use by a single application. Regular dialy use is essential to obtain maximum bacterial reduction.

The product of this invention is based on the concept that antiseptic preparation should reduce the bacterial population on the very first application, and not depend on repeated use for its activity. The considerable advantage Killing dilutions were run on the preceding compositions by the method given in the Official Methods of Analysis of the Association of Ofiicial Agricultural Chemists, Ninth Edition (1960), page 63 et seq., using as test organisms both Staphylococcus aureus and Salmonella typhosa. Killing dilutions against these organisms were found to be as great or greater than the corresponding killing dilutions of the quaternary by itself.

Example 11 11 respectively using hydrochloric acid or sodium hydroxide to obtain the appropriate levels.

Killing dilutions were run on these compositions with the same results as described in Example I.

7 Example III Parts .Cetyl dimethyl amine oxide, 30% 5.0

N-lauryl N-methyl glycine, 30% 12.0 Alkyl 1 dimethyl benzyl ammonium chloride, 50% 0.5 Alkyl dimethyl ethyl-benzyl ammonium chloride,

50% Water Balance Example IV Lauryl dimethyl amine oxide, 30 35.0 Stearyl dimethyl amine oxide, 30% 9.0 Quaternary ammonium germicide blend of equal amounts of the alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethyl-benzyl ammonium chloride of Example III, 50% 1.0 Hydroxyethyl cellulose 0.5 Acctylated lanolin 0.5

Water to make 100.0.

This was adjusted to a pH of 6.0 to give a nonirritating surgical scrub having a pleasing slip and emollient efiect on the hands.

Example V The degerming product of Example IV was tested by a modification of the Quinn split-glove technique cited above. Ivory soap was used as a control. The test was carried out as follows:

1500 cc. of tap water was charged into a sterilized basin (basin #1). 1 and 2 cc. portions were removed for plating (correction for blank). 500 cc. of Azolectin (lecithin) and Tween (polyoxyethylene sorbitan monoleate) neutralizer were added to the basin to inactivate the quaternary. A sterile surgical glove was placed on one hand and both hands were then moistened in the basin; Both hands were raised above Water level and cupped together and 2.0 cc. of the composition of Example IV was poured on the hands. The subjectjthen began to work up a lather and. scrubbed the ungloved hand with a sterile brush for 2 /2 minutes. The subject rinsed for 15 seconds and the hands were allowed to drip over the basin. The procedure was repeated again with 2.0 cc. of the degerming composition of Example IV for 2 /2 minutes followed by-15 seconds rinsing which concludes basin #1. and allowed to set for 30 seconds to one minute before plating.

Thereafter the hands were rinsed three times as follows:

Basin #2, #3, and #4 each received 2000 cc. of tap water in sequence and were used to washin the same manner as basin #1, except that the test hand used Ivory Soap (8% aqueous sterile solution) and no neutralizer. At the conclusion, the glove was removed, a fresh one placed on the opposite hand, and the entire procedure repeated exclusively with Ivory Soap solution.

1 cc. from each wash was plated in duplicate into Tryptone Glucose Extract Agar. Subsequent dilutions from each basin were made as deemed necessary so as to obtain good countable plates. The standard plate count method was followed in each case.

Similarly, a commercially available hexachlorophene detergent sanitizer (Phisohex), with Ivory Soap as a control as before. A new panel of subjects was employed.

The following tables indicate the number of organisms counted in a culture of 1 cc. of the wash water in each case, and also the percentage reduction per basin as compared with the control.

TABLE II Test preparation: Degerming composition of Example IV. Control: Ivory soap.

[Counts of organisms per cc.]

Basin No. Subject 1 Test"- 2, 000 1, 129, 500 2, 310, 000 642, 500 Control 21, 700, 000 10, 815, 000 2, 160, 000 2, 450 000 Percent Reduction-- 99. 99 89.6 73. s 2 Test 2, 0 72, 000 77, 009 95,

Control S, 100, 000 675, 000 620, 500 598, 009 Percent Reduction 99. 97 89. 3 87. 6 84. 1 3- Test- 19, 000 32, 000 38, 000 38, 000 Contr 3, 760, 000 95, 000 104, 000 82, 000 Percent Reduction 99. 5 66. 3 63. 5 43. 7 4 Test 2, 000 3, 000 2, 000 6, 000 Control 5, 690, 000 126, 000 117, 000 88, 000 Percent Reduction.-- 99.96 97. 6 88.3 93. 2 5 est 36, 000 120, 000 615, 000 319,500 Control 10, 600, 000 2, 110, 000 2, 140, 000 587, 000 99. 66 94. 3 71. 45. 6 st 916, 000 110, 000 107, 000 417, 000 7, 180, 000 131, 000 5, 040, 000 165, 000 Percent Redueti0n 87. 25 16. 03 97. 88 7 Test 94, 000 460, 500 151, 000 148, 000 a Control 4, 210, 000 1, 990, 000 375, 000 485, 500 1 Percent Reduction. 97. 77 79. 59. 79 69. 51 8 Test 367, 500 1, 050, 500 499, 500 890, 000 r 3, 020, 000 547, 500 748, 500 623, 500 I 87. 91. 33. 28 42. 74 111, 000 2, 000 2, 000 2, 000 Control 2, 200, 000 23, 000 50, 000 45, 000 Percent Reduction-.- 95 91. 4 96 95. 6 l0 Test 55, 000 2, 000 2, 000 2, 000 Control 300, 000 495, 000 261, 000 133, 000 Percent Reduction 81. 7 99 9 99. 4 99. 5

The brush was left in the basin TABLE III Test preparation: Phisohex. Control: Ivory soap.

[Counts of organisms per cc.]

Basin No. Subject 1 Test 2, 040, 000 844, 000 430, 000 342, 000 G011 310, 000 258, 000 154, 000 40, 000 Percent Reduction- 2 e 310, 000 262, 000 1, 580, 000 476, 000 Con 126, 000 42, 000 32, 000 62, 000 Percent Reduc i n 3 e 358, 000 168, 000 212, 000 202, 000 Con 3, 280, 000 2, 346, 000 1, 186, 000 810, 000 89 94 82 75 2, 670, 000 1, 130, 000 730, 000 326, 000 1, 370, 000 890, 000 548, 000 302, 000

3, 234, 000 3, 954, 000 1, 254, 000 722, 000 ol 1, 560, 000 994, 000 894, 000 624, 000 Percent Ber'hintinn 6 Test 1, 010, 000 392, 000 374, 000 292, 000 Control 434, 000 124, 000 82, 000 176, 000 Percent F orln r tirm 7 Test 1, 070, 000 920, 000 1, 060, 000 830, 000 Control 1, 190, 000 940, 000 790, 000 376, 000 Percent Reduct 8 Test 1, 226, 000 76, 000 68, 000 58, 000 Control- 270, 000 82, 000 64, 000 110, 000 Percent Reduetiom--. 47, 2 9 Test 730, 000 550, 000 308, 000 332, 000 Control 3, 570, 000 2, 040, 000 1, 590, 000 1, 230, 000 Percent Reduction. 79. 6 78. 81 74 10 Test 45, 706, 000 42, 206, 000 37, 206, 000 17, 506, 000 Control 9, 600, 000 6, 106, 000 5, 7 06, 000 7, 606, 000 Percent Boflnetinn The above data show that the very first scrubbing with the products of this invention results in a great diminution of the bacterial count in the washings amounting to more than 95%; and that subsequent washings with an ordinary soap continue to show further diminution as compared with the use of soap alone. It will thus be apparent that a single application as a surgical scrub is remarkably effective in degermin g the hands by an extremely high percentage.

When the widely used hexachlorophene type of degerming detergent is used, however, the count after the scrubbing is of a greater order of magnitude, and further washings with soap causes no further diminution in the count as compared with soap alone throughout; in fact, ordinary soap appears superior as a de-germing agent in the second, third and fourth washings, simply by force of mechanically removing some of the residual viable organisms.

The products of this invention thus surprisingly effect the said very considerable reduction in the skin microbial level on the first application, and they do not depend upon continued or repeated use for their activity. This is in marked contrast with the commonly used surgical scrubs which specifically call for repeated use in order to build up the degerming effect, which effect may be cancelled out by the subsequent use of ordinary detergents such as soap, or by washing with solvents such as alcohol.

Example V1 Parts Cetyl dimethyl amine oxide, 10.00 N-lauryl N-methyl glycine 30.00 Lauryl isoquinolinium bromide, 75% 0.25 Water Balance for example, as distearyl dimethyl ammonium chloride or methosulfate, distearyl methyl polyethoxyethyl a-rnmonium chloride or methosulfate or the corresponding quaternary ammonium salts in which the two long alkyl radicals are mixtures of the fatty radicals present in the alcohols obtained by hydrogenation of tallow. We may also use the corresponding dialkyl quaternary ammonium chlorides or methosulfates in which the alkyl radicals are largely cetyl, myristyl or lauryl. We prefer to use quaternaries of the aforementioned types in which the two alkyl radicals are derived from hydrogenated tallow. Other softeners suitable for incorporation in our composition include the well-known imidazoline types long used by textile mills as permanent softeners such, for example, as those prepared by condensation of approximately one mole of stearic acid with one mole of diethylene triamine or of hydroxyethyl ethylene diamine with the elimination of sufiicient water during reaction to form, in large part, an imidazoline ring having, for example the following structure:

and in which compounds quaternization of at least one of the nitrogen atoms is effected with acetic anhydride, diethyl sulfate, triethyl phosphate or phosphite 01' the like. The preparation of various compounds of this nature is described in U.S.P. 2,200,815. Other softeners of similar nature are obtainable by reaction of about one mole of imidazoline derived from the condensation of stearic acid with a mole of diethylene triamine and subsequent reaction of the product with urea, under heat, whereby ammonia is eliminated and a complex urea derivative of the imidazoline is formed which may subsequently be dissolved in acid or quaternized wit-h dimethyl sulfate, diethyl sulfate, triethyl phosphate or phosphite, acetic anhydride, benzyl chloride and the like. The preparation of such products is described in U.S.P. 2,304,369.

salt content deposited on urea 0.5 (3) Dialkyl 3 dimethyl ammonium methosulfate, in

the form of a powder containing 40% active cationic softener content deposited on urea 2.5 (4) Sodium tripolyphosphate 59.0 (5) Sodium metasilicate pentahydrate 4 1 0.0 (6) Sodium acid pyrophosphate 13.0

1 Alkyl distribution: 60% C14, 30% C1 5% C1 5% C18.

'-Alkyl distribution: 50% C1 3 a C14, 17% C1 3% C18.

The alkyl radicals being those derived by hydrogenation lii i s o Granular, sold by Philadelphia Quartz Company.

The powders of the above formulation, i.e. items 2 through 6, were charged into a clean stainless steel sigmablade mixer capable of being steam heated and the temperature of the contents was raised to about 40 C. while being thoroughly mixed.

In a separate vessel, the stearyl dimethyl amine oxide was diluted with about an equal volume of methanol with warming. This solution was then slowly added to the blended powders while mixing was continued.

The wet slurry thus formed was heated to 85-90 C. with mixing in order to volatilize the alcohol and the water content of the amine oxide.

Mixing with heating was continued until the mass became hard and brittle, breaking up into a powder under the action of the sigma blades. The powder was allowed to dry in the air in pans and then com-minuted, being passed through a 200 mesh screen.

We claim:

1. A germicidal agent consisting essentially of (1) at least one tertiary amine oxide of the formula:

RNRR" wherein R is a member of the group consisting of alkyl and alkenyl having 8 to 20 carbon atoms, and wherein R and R" are selected from the group consisting of methyl, ethyl, propyl, isopropyl, hydroxyalkyl, hydroxyalkoxyalkyl, hydroxyalkyl polyalkoxyalkyl, and morpholine containing R, R and N as members, the alkyl, the hydroxyalkyl compounds being lower alkyl, and (2) at least one germicidal quaternary ammonium compound having at least one long chain alkyl group of 8 to 22 carbon atoms attached to the quaternary nitrogen and having a phenol coefficient of at least 100 with respect to Staphylococcus aureus and Salmonella typhosa at 20 C., the amine oxide and quaternary ammonium compound being respectively present in the proportion of about 50:1 to about :1 parts by weight.

2. The composition of claim 1 wherein the amine oxide is stearyl dimethyl amine oxide and the quaternary ammonium compound is alkyl dimethyl benzyl ammonium chloride wherein the alkyl has 12 to 18 carbon atoms.

3. The composition of claim 1 wherein the amine oxide is cetyl dimethyl amine oxide, the quaternary ammonium compound is lauryl isoquinolinium bromide and wherein N-lauryl N-methyl glycine is present in an amount of about three times that of the amine oxide.

4. The composition of claim 1 wherein the amine oxide is stearyl dimethyl amine oxide and the quaternary ammonium compound is a mixture of alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethyl-benzyl ammonium chloride wherein the alkyls each contain from 12 to 18 carbon atoms.

5. The composition of claim 1 wherein the amine oxide is a mixture of myristyl dimethyl amine oxide and cetyl dimethyl amine oxide, and the quaternary ammonium compound is a mixture of alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethyl-benzyl ammonium chloride wherein the alkyls each contain from 12 to 18 carbon atoms.

6. The composition of claim 1 wherein the amine oxide is a mixture of lauryl. dimethyl amine oxide and stearyl dimethyl amine oxide, the quaternary ammonium com- 1 pound is a mixture of alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethyl-benzyl ammonium chlo- I ride wherein the alkyls each have 12 to 18 carbon atoms,

and wherein the composition also includes hydroxyethyl cellulose and acetylated lanolin, each in an amount of about one-half that of the quaternary ammonium compound mixture.

7. The composition of claim 1 wherein the pH is from 4.0 to 11.0.

8. The composition of claim 1 including a cellulose softener agent selected from the group consisting of di higher alkyl dimethyl ammonium halides and methosulfates and higher alkyl imidazolines, said higher alkyls having 11 to 18 carbon atoms.

9. A method of simultaneously cleaning and sterilizing human tissue which comprises applying to said tissue a composition consisting essentially of (1) at least one tertiary amine oxide of the formula:

wherein R is a member of the group consisting of alkyl and alkenyl having 8 to 20 carbon atoms, and wherein R and R are selected from the group consisting of methyl, ethyl, propyl, isopropyl, hydroxyalkyl, hydroxyalkoxyalkyl, hydroxyalkyl polyalkoxyalkyl, and morpholine containing R, and R" and N as members, the alkyl of the hydroxyalkyl compounds being lower alkyl, and (2) at least one germicidal quaternary ammonium compound having at least one long chain alkyl group of 8 to 22 carbon atoms attached to the quaternary nitrogen and having a phenol coefiicient of at least with respect to Staphylococcus aureus and Salmonella typhosa at 20 C., the amine, oxide and quaternary ammonium compound being present in the proportion of about 50:1 to about 5:1 parts by weight.

10. The method of claim 9 wherein said composition consists essentially of stearyl dimethyl amine oxide, alkyl dimethyl benzyl ammonium chloride in which the alkyl distribution corresponds to 60% C 30% C 5% C and 5% C and alkyl dimethyl ethyl-benzyl ammonium chloride in which the alkyl distribution corresponds to C12, C14, C16 and C18, thfi COIIIPO- nents being present in suificient amounts to establish germicidal effectiveness.

11. The method of claim 9 wherein said composition consists essentially of myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, alkyl dimethyl benzyl ammonium chloride in which the alkyl distribution corresponds to C14, C16, C12 and 5% C13, and dimethyl ethyl-benzyl ammonium chloride in which'the alkyl distribution corresponds to 50% C 30% C 17% C and 3% C the components being present in sufficient amounts to establish germicidal efiectiveness.

12. The method of claim 8 wherein said composition consists essentially of cetyl dimethyl amine oxide, alkyl dimethyl benzyl ammonium chloride wherein the alkyl group has 8 to 20 carbon atoms, alkyl dimethyl ethylbenzyl ammonium chloride wherein the alkyl group has 8 to 20 carbon atoms, and, additionally, N-lauryl-N-methyl glycine in about three times the amount of the amine oxide and having a pH of 6.0, the components being present in suflicient amounts to establish germicidal effectiveness.

13. The method of claim 9 wherein said composition consists essentially of lauryl dimethyl amine oxide, stearyl dimethyl amine oxide, alkyl dimethyl benzyl ammonium chloride wherein the alkyl group has 8 to 20 carbon atoms, alkyl dimethyl ethyl-benzyl ammonium chloride where 13 the alkyl group has 8 to 20 carbon atoms, and, additionally hydroxyethyl cellulose and acetylated lanolin, each in about one-half the amount of the total amount :of quaternary ammonium compounds, the components being present in sufficient amounts to establish germicidal ef- 5 fectlveness.

References Cited by the Examiner UNITED STATES PATENTS 2,953,526 9/1960 Bergman et a1 252-8.8 10 3,085,982 4/1963 Steer et a1. 252-137 3,086,943 4/1963 Lang 252-452 14 FOREIGN PATENTS 8/ 1953 Canada.

OTHER REFERENCES Detergents and E-mulsifiers, 1963 Annual, John W. McCutcheon, Inc., NJ. (1963), p. 32.

Surface Active Agents, Vol. 1, Schwartz et al., Interscience PubL, NY. (1949), p. 235.

LEON D. ROSDOL, Primary Examiner.

ALBERT T. MEYERS, DONALD E. CZAJA, Examiners.

S. E. DARDEN, Assistant Examiner. 

1. A GERMICIDAL AGENT CONSISTING ESSENTIALLY OF (1) AT LEAST ONE TERTIARY AMINE OXIDE OF THE FORMULA:
 9. A METHOD OF SIMULTANEOUSLY CLEANING AND STERILIZING HUMAN TISSUE WHICH COMPRISES APPLYING TO SAID TISSUE A COMPOSITION CONSISTING ESSENTIALLY OF (1) AT LEAST ONE TERTIARY AMINE OXIDE OF THE FORMULA: 